Synergistic herbicidal composition and use thereof

ABSTRACT

A herbicidal composition is provided, the composition comprising: (A) the crystalline modification I of 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione (mesotrione); and (B) the crystalline modification I of methyl 2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate (mesosulfuron-methyl). A method of controlling undesirable plant growth at a locus comprises applying to the locus herbicidally effective amounts of both (A) the crystalline modification I of 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione (mesotrione); and (B) the crystalline modification I of methyl 2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate (mesosulfuron-methyl).

BACKGROUND

1. Field

The present disclosure relates to a synergistic herbicidal compositioncontaining mesotrione and mesosulfuron-methyl, each in particularcrystal modifications. The composition finds use in controlling thegrowth of undesirable plant, particularly in crops, including using theaforementioned composition.

2. Description of Related Art

The protection of crops from undesirable plant, which inhibits cropgrowth, is a constantly recurring problem in agriculture. To solve thisproblem, researchers are trying to produce an extensive variety ofchemicals and chemical formulations effective in the control of suchundesirable growth. Chemical herbicides of many types have beendisclosed in the literature and a large number are in commercial use.

Some herbicidal active ingredients have been shown to be more effectivewhen applied in combination rather than applied individually, thiseffect being referred to as “synergism.” According to Herbicide Handbookof the Weed Science Society of America, Seventh Edition, 1994, page 318,“synergism” is an interaction of two or more factors such that theeffect when combined is greater than the predicted effect based on theresponse to each factor applied separately.

The compound 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione has thecommon name “mesotrione”. Mesotrione is a substance that can formpolymorph crystals. Two different forms, crystalline modifications I andII, of mesotrione are described in WO2006021743, which is incorporatedherein by reference for all purposes. Mesotrione is active as aherbicide and is now commercially available in a range of formulationsfor controlling the growth of undesirable plant.

The compound methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate,having the common name “mesosulfuron-methyl”, is a member of thesulfonylurea group of chemicals. Mesosulfuron-methyl is a potentherbicide having high selectivity, high efficiency, low toxicity andother desirable attributes. It is used post-emergence on crops, such aswheat and cereals, against a variety of annual and perennial grasses andbroadleaved weeds. It is rather less toxic towards algae and is ofgenerally low toxicity towards most wildlife.

The commercially available mesosulfuron-methyl, which is usuallymanufactured by the process described in U.S. Pat. No. 5,648,315, whichis incorporated by reference for all purposes, is present in anamorphous state.

It has been found that mesosulfuron-methyl in the amorphous state ishighly unstable. It will generally undergo significant hydrolysis whendissolved or dispersed in water. Furthermore, hydrolysis can occurduring storage, particularly where the compound is exposed to moisture.It has been found that a crystalline form of mesosulfuron-methyl, termedhereinafter “crystalline modification I”, has an improved stability informulations (U.S. Ser. No. 14/957,768, filed on even date herewith, andincorporated herein by reference for all purposes. The crystallinemodification I of mesosulfuron-methyl of the invention exhibits at least3 of the following reflexes as 20 values in an X-ray powderdiffractogram recorded using Cu-Kα radiation at 25° C.:2θ=5.41±0.2  (1)2θ=10.26±0.2  (2)2θ=10.88±0.2  (3)2θ=12.14±0.2  (4)2θ=16.38±0.2  (5)2θ=18.87±0.2  (6)2θ=19.47±0.2  (7)2θ=20.82±0.2  (8)2θ=21.88±0.2  (9)2θ=22.55±0.2  (10)2θ=22.96±0.2  (11)2θ=23.22±0.2  (12)2θ=24.10±0.2  (13)2θ=24.50±0.2  (14)2θ=26.35±0.2  (15)

SUMMARY

It has been surprisingly found that combining the crystallinemodification I of mesotrione with the crystalline modification I ofmesosulfuron-methyl provides a composition having a synergisticactivity, that is, an increased herbicidal activity, compared with theactivity expected from the activity of the two components when appliedindividually.

The XRD diffraction data for mesotrione crystal form I given by WO2006/021743 are given below, although some peak shifting is possible.

Peak Position (2-Theta) Peak Position (d spacing)  8.52 10.34  17.085.18 17.43 5.08 18.74 4.73 19.04 4.66 19.31 4.59 19.52 4.54 21.15 4.2025.73 3.46 28.66 3.11

Alternatively, the crystalline modification I mesotrione may have aslightly shifted XRD spectrum:

Peak Position (2-Theta) Peak Position (d spacing)  8.44 10.47  17.355.11 17.55 5.05 18.67 4.75 18.98 4.68 19.24 4.61 19.45 4.56 21.06 4.2225.64 3.47 28.55 3.13

Accordingly, in a first aspect, the invention provides a herbicidalcomposition comprising:

(A) the crystalline modification I of2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione (mesotrione); and

(B) the crystalline modification I of methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate(mesosulfuron-methyl).

The composition of an embodiment of the invention is of particular usefor controlling the growth of undesirable plant.

In a second aspect, the invention provides a method of controlling thegrowth of undesirable plant comprising applying to the plant or to thelocus thereof a herbicidally effective amount of the herbicidalcomposition of the first aspect of the present invention.

In a further aspect, the invention provides the use of the herbicidalcomposition of the first aspect of the invention in control ofundesirable plant growth at a locus.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an infrared (IR) spectrograph of crystalline modification I ofmesosulfuron-methyl, according to an embodiment of the invention.

FIG. 2 is an X-ray powder diffractogram (XRD) of crystallinemodification I of mesosulfuron-methyl, according to an embodiment of theinvention.

FIG. 3. is a Differential Scanning calorimetry (DSC) spectrum ofcrystalline modification I of mesosulfuron-methyl, according to anembodiment of the invention.

FIG. 4 is an X-ray powder diffractogram of amorphousmesosulfuron-methyl.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

The references to the crystalline modifications I and II of mesotrioneas used herein, refer to the crystalline modification of mesotrionedisclosed in WO2006/021743, which is incorporated herein by reference inits entirety, where they are described as Form I and Form II,respectively.

The term “herbicide” as used herein, refers to a compound that controlsthe growth of plants.

The term “herbicidally effective amount” as used herein, refers to thequantity of such a compound or combination of such compounds that iscapable of producing a controlling effect on the growth of plants. Thecontrolling effects include all deviation from the natural developmentof the target plants, for example killing, retardation of one or moreaspects of the development and growth of the plant, leaf burn, albinism,dwarfing and the like.

The term “plants” refers to all physical parts of a plant, includingshoots, leaves, needles, stalks, stems, fruit bodies, fruits, seeds,roots, tubers and rhizomes.

The term “locus” refers to the place on which the plants are growing,the place on which the plant propagation materials of the plants aresown or the place on which the plant propagation materials of the plantswill be sown.

“At least one” designates a number of the respective compounds orcomponents of 1, 2, 3, 4, 5, 6, 7, 8, 9 or more, preferably 1, 2, or 3.

The synergistic herbicidal composition, the method and use of thepresent invention are suitable for controlling undesirable plant growthin a range of crops, including: cereals, for example wheat, barley, rye,oats, corn, rice, sorghum, triticale and related crops; fruit, such aspome fruit, stone fruit and soft fruit, such as apples, pears, plums,peaches, pistachio, almonds, cherries, and berries, for example grape,banana, strawberries, bushberry, cranberries, raspberries, blackberriesand blueberries; leguminous plants, for example beans, lentils, peas,and soybeans; oil plants, for example oilseed rape, mustard andsunflowers; cucurbitaceae, for example cantaloupe, marrows, cucumbers,melons, pumpkin, squash and watermelon; citrus fruit, such as oranges,lemons, grapefruit and mandarins; and vegetables, for example spinach,lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes,paprika, garlic and leeks; coffee; sugarcane; hops; tree nuts; as wellas ornamentals, for example flowers, such as roses, shrubs, broad-leavedtrees and evergreens, such as conifers. Preferably, the compositiondescribed herein is used to treat cereals, fruits and vegetables. Morepreferably, the composition described herein is used to treat wheat,corn, sorghum, asparagus, blueberries and cranberries.

The control of undesirable plant growth in such crops may be achieved byapplying to the locus (A) the crystalline modification I of2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione (mesotrione), which isidentified as Form I in WO 2006/021743 and (B) the crystallinemodification I of methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate(mesosulfuron-methyl) in suitable amounts.

The active compounds (A) and (B) may be applied to the locus together orseparately. If applied separately, active compounds (A) and (B) may beapplied at the same time and/or consecutively. The control may compriseapplying to the undesirable plant or the locus thereof a herbicidallyeffective amount of the herbicidal composition.

It has been surprisingly found that a combination of (A) the crystallinemodification I of 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione(mesotrione) and (B) the crystalline modification I of methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate(mesosulfuron-methyl) exhibits a synergistic action in the control ofmany weeds, particularly, but not limit to, broadleaved weeds, grassesand sedges. For example, weeds treatable according to an embodiment ofthe invention include:

black mustard, blue/purple mustard, broadleaf dock, bur buttercup, bushywallflower, Carolina geranium, Centella, Cinquefoil, clasping pepperwee,Coast fiddleneck, common buckwheat, Common Mallow, common radish,conical catchfly, corn chamomile, corn spurry, Creeping Oxalis, CreepingSpeedwell, cress, Dichondra, false chamomile, field chickweed, fieldpennycress, fixweed, groundsel, London rocket, marshelder, mayweedchamomile, miners lettuce, narrowleaf lambsquarters, nightfloweringcatchfly, Pennsylvania smartweed, pigweed, pineappleweed, plainscoreopsis, prickly lettuce, redmaids, Russian thistle, scentlesschamomile, smallflower buttercup, smartweed, snow speedweed, stickychickweed, stinking mayweed/dogfennel, swinecress, tansymustard, tarweedfiddleneck, tumble, volunteer lentils, volunteer peas, volunteersunflower, waterpod, wild chamomile, wild garlic, wild radish, IndianMallow (Abutilon incana); Velvetleaf (Abutilon theophrasti); HophornbeamCopperleaf (Acalypha ostryaefolia); Virginia Copperleaf (Acalyphavirginica); Common Yarrow (Achillea millefolium); Alligatorweed(Alternantha philoxeroides); Khakiweed (Alternanthera pungens); Pigweed,Tumble (Amaranthus albus); Pigweed, Prostrate (Amaranthus blitoides);Livid Amaranth (Amaranthus blitum); Pigweed, smooth (Amaranthushybridus); Amaranth, palmer (Amaranthus palmeri); Amaranth, powell(Amaranthus powellii); redroot pigweed (Amaranthus retroflexus); CommonWaterhemp (Amaranthus rudis); Spiny Pigweed (Amaranthus spinosus);Amaranth (Amaranthus spp); waterhemp (Amaranthus tuberculatus);Huisachedaisy (Amblyolepis setigera); Common Ragweed (Ambrosiaartemiisifolia); common ragweed (Ambrosia artemisiifolia); WoollyleafBursage (Ambrosia grayi); Western Ragweed (Ambrosia psilostachya); greatragweed (Ambrosia trifida); Toothcup (Ammannia latifolia); Spurred Anoda(Anoda cristata); Hemp Dogbane (Apocynum cannabinum); Common Burdock(Arctium minus); Mexican-Poppy (Argemone mexicana); Annual Pricklepoppy(Argemone polyanthemos); Silversage (Artemesia ludoviciana); CommonMilkweed (Asclepias syriaca); Antelope Horn (Asclepias viridis); SlenderAster (Aster gracilis); White Heath Aster (Aster pilosus); common orache(Atriplex patula); Wild oats (Avena spp.); Yellow Rocket (Barbareavulgaris); Common Beggar-tick (Bidens alba); Mustard, wild (Brassicakaber); Brome grass (Bromus diandrus); Sprawling Horseweed(Calyptocarpus vialis); Smallseed Falseflax (Camelina microcarpa);Trumpetcreeper (Campsis radicans); Hemp (Cannabis sativa); Marijuana(Cannabis spp.); Shepherd's Purse (Capsella bursa-pastoris);Bittercress, Smallflowered (Cardamine arviflora); Thistle, Musk (Carduusnutans); sedges (Carex spp.); Thistle, Distaff (Carthamus lanatus);Partridgepea (Cassia chamaecrista); SilverLeaf Cassia (Cassiaphyllodinea); Thistle, Malta Star (Centaurea melitensis); MouseearChickweed (Cerastium vulgatum); False Nightshade (Chamaesarachacoronopus); Garden Spurge (Chamaesyce hirta); Hyssop Spurge (Chamaesycehyssopifolia); Common Lambsquarters (Chenopodium album); Atriplex(Chenopodium orach); goosefoots (Chenopodium spp.); Oxeye Daisy(Chrysanthemum leucanthemum); Chicory (Cichorium intybus); Waterhemlock(Cicuta maculata); Thistle, Tall (Cirsium altissimum); Canada Thistle(Cirsium arvense); Thistle, Texas Purple (Cirsium texanum); Bull Thistle(Cirsium vulgare); Texas Bullnettle (Cnidoscolus texanus); BastardToadflax (Comandra umbellata); Dayflower (Commelina); SpreadingDayflower (Commelina diffusa); Poison Hemlock (Conium maculatum);Bindweed, Field (Convolvulus arvensis); Bindweed, Texas (Convolvulusequitans); Bindweed, Hedge (Convolvulus sepium); Horseweed (marestail)(Conyza canadensis); Horseweed (Conyza canadensis); Rain Lily (Cooperiadrummondii); Coreopsis (Coreopsis tinctoria); Scrambledeggs (Corydaliscurvisiliqua); Croton, Woolly (Croton capitatus); Croton, Tropic (Crotonglandulosus); Croton, Texas (Croton texensis); Buffalo Gourd (Cucurbitafoetidissima); Field Dodder (Cuscuta campestris); Marsh Parsley(Cyclospermum leptophylum); Nutsedge, yellow (Cyperus esculentus);Jimsonweed (Datura stramonium); Carrot, wild (Daucus carota); WildCarrot (Daucus carota); Mustard, Tansy (Descurainia pinnata); Mustard,Pinnatetansy (Descurainia pinnate); Flixweed (Descurainia sophia);Illinois Bundleflower (Desmanthus illinoensis); Creeping Beggarweed(Desmodium incanum); Beggarweed (Desmodium spp.); Crabgrass, large(Digitaria sanguinalis); False Daisy or Eclipta (Eclipta prostrata);Cupid's Shaving Brush (Emilia sonchifolia); Englemann Daisy (Englemanniapinnatifida); Daisy Fleabane (Erigeron annuus); Filaree, Calif. orRedstem (Erodium cicutarium); Filaree, Texas or Storkbill (Erodiumtexanum); Garden Rocket (Eruca vesicaria ssp. sativa); Wright Eryngo(Eryngium heterophyllum); Rattlesnake master (Eryngium yuccifolium);Bushy Wallflower (Erysimum repandum); White Snakeroot (Eupatoriumrugosum); Dogfennel (Euphorbia capillifolium); Spurge, Toothed(Euphorbia dentata); Spurge, Leafy (Euphorbia esula); Spurge, Prostrate(Euphorbia humistrata); Snow-on-the-mountain (Euphorbia marginata);Nodding Spurge (Euphorbia nutans); Ground Spurge (Euphorbia prostrata);Indian Blanket (Gaillardia pulchella); Galinsoga (Galinsoga parviflora);Catchweed Bedstraw (Galium aparine); Scarlet Gaura (Gaura coccinea);Lizardtail Gaura (Gaura Parviflora); Wild Geranium (Geraniumcarolinanum); Red Hornedpoppy (Glaucium corniculatum); Wandering Cudweed(Gnaphalium pensylvanicum); Curlycup Gumweed (Grindelia quarrosa);Annual Broomweed (Gutierrezia dracunculoides); Common Sneezeweed(Helenium amarum); Bitterweed, Brown (Helenium badium); SmallheadSneezeweed (Helenium microcephalum); Common Sunflower (Helianthusannuus); Texas Blueweed (Helianthus ciliaris); Jerusalem Artichoke(Helianthus tuberosus); Camphorweed (Heterotheca subaxillaris); VeniceMallow (Hibiscus trionum); Hogpotato (Hoffmanseggia densiflora); Barleygrass (Hordeum leporinum); Japanese Hops (Humulus japonicus);Woollywhite, Yellow (Hymenopappus flavescens); Woollywhite, Chalkhill(Hymenopappus tenuifolius); Bitterweed (Hymenoxys odorata); Balsam Gourd(Ibervillea lindheimeri); Creeping Indigo (Indigofera spicata);Sweet-potato (Ipomea batatas); Morningglory, ivyleaf (Ipomoeahederacea); Morningglory, entireleaf (Ipomoea hederacea var.integriuscula); Morningglory, pitted (Ipomoea lacunosa); Morningglory,Bigroot (Ipomoea pandurata); Morningglory, Tall (Ipomoea purpurea);Morningglory, Sharppod (Ipomoea trichocarpa); toad rush (Juncusbufonlus); Canada Rush (Juncus Canadensis); Soft rush (Juncus effuses);slender rush (Juncus tenuis); Hairy Caltrop (Kallstroemia hirsutissina);Kochia (Kochia scoparia); Wild Lettuce (Lactuca serriola); Henbit(Lamium amplexicaule); Deadnettle, Purple (Lamium purpureum); Lantana(Lantana camara); Virginia Pepperweed (Lepidium virginicum); Bladderpod(Lesquerella gracilis); Corn Gromwell (Lithospermum arvense); Annualryegrass (Lolium rigidum); Honeysuckle (Lonicera spp.); BirdsfootTrefoil (Lotus corniculatus); Long Fruited Primrose-Willow (Ludwigiaoctovalvis); Skeletonweed (Lygodesmia juncea); Purple Loosestrife(Lythrum salicaria); Tahoka Daisy (Machaeranthera tanacetifolia); AlkaliMallow (Malvella leprosa); Horehound (Marrubium vulgare); Bur Clover(Medicago hispida); Black Medic (Medicago lupulina); Blackfoot Daisy(Melampodium leucanthum); Yellow Sweetclover (Melilotus indica);Creeping Cucumber (Melothria pendula); annual mercury (Mercurialisannua); Climbing Hempweed (Mikania scandens); Carpetweed (Mollugoverticillata); Balsam-Apple (Momordica charantia); Purple Horsemint(Monarda citriodora); Mousetail (Myosurus minimus); Waterleaf (Namahispidum); Scarlet Musk Flower (Nyctaginia capitata); CutleafEveningprimose (Oenothera laciniata); Thistle, Scotch (Onopordumacanthium); Prickly Pear (Opuntia spp.); Creeping Woodsorrel (Oxaliscorniculata); Florida Pellitory (Parietaria floridana); Santa Maria orParthenium Pancake Weed (Parthenium hysterophores); Virginia Creeper(Parthenocissus quinquefolia); African Rue (Peganum Harmala); WhiteFoxglove Beardtongue (Penstemon digitalis); Annual phalaris, paradoxagrass (Phalaris paradoxa); Match-Head (Phyla nodiflora); Chamberbitter(Phyllanthus urinaria); Cutleaf Groundcherry (Physalis angulata); ClammyGroundcherry (Physalis heterophylla); Purple Flower Groundcherry(Physalis lobata); Smooth Groundcherry (Physalis subglabrata); CommonPokeweed (Phytolacca americana); Bracted Plantain (Plantago aristata);Buckhorn Plantain (Plantago lanceolata); Blackseed Plantain (Plantagorugelii); Broadleaf Plantains (Plantago spp.); Saltmarsh Fleabane(Pluchea odorata); Silversheath Knotweed (Polygonum argyrocoleon);Prostrate Knotweed (Polygonum aviculare); Wild Buckwheat (Polygonumconvolvulus); Smartweed, Pale (Polygonum lapathifolium); Smartweed,Pennsylvania (Polygonum pensylvanicum); knotweed (polygonum spp.);Common Purslane (Portulaca oleracea); cinquefoil (Potentilla spp.);Sawtooth aster (Prionopsis ciliata); Devil's Claw (Proboscidealouisianica); Mock Bishop's Weed (Ptilimnium capillaceum); Kudzu(Pueraria spp.); Carolina False Dandelion (Pyrrhopappus carolinianus);Bulbous Buttercup (Ranunculus bulbosus); creeping buttercup (Ranunculusrepens); Mustard, Turnip Weed (Rapistrum rugosum); Mexicanhat (Ratibidacolumnaris); Smooth Sumac (Rhus glabra); Multiflora rose (Rosamultiflora); Curly Dock (Rumex crispus); Lanceleaf Sage (Salvaniareflexa); Elderberry (Sambucus canadensis); annual knawel (Scleranthusannuus); Butterweed (Senecio glabellus); Threadleaf Groundsel (Seneciolongilobus); Riddell Groundsel (Senecio riddellii); Common Groundsel(Senecio vulgaris); Sicklepod (Senna obtusifolia); Twinleaf Sennia(Senna roemeriana); Hemp Sesbania (Sesbania exaltata); Burcucumber(Sicyos angulatus); Southern Sida (Sida acuta); Prickly Sida (Sidaspinosa); Rosinweed (Silphium integrifolium); Compass Plant (Silphiumlaciniatum); Cup Plant (Silphium perfoliatum); Thistle, Blessed Milk(Silybum marianum); wild mustard (Sinapis arvensis); Mustard, Tumble(Sisymbrium altissimum); Mustard, London Rocket (Sisymbrium irio);Greenbriar (Smilax spp.); Black Nightshade (Solanum americanum);Horsenettle (Solanum carolinense); Silverleaf Nightshade (Solanumelaeagnifolium); Nightshade, black (Solanum nigrum); Nightshade, Easternblack (Solanum ptycanthum); Buffalobur (Solanum rostratium); HairyNightshade (Solanum sarrachoides); black nightshade (Solanum spp);Goldenrod (Solidago spp.); Spiny Sowthistle (Sonchus asper); AnnualSowthistle (Sonchus oleraceus); Bushy Buttonweed (Spermacoce assurgens);Orange Globe Mallow (Sphaeralcea occidentalis); Common Chickweed(Stellaria media); Dandelion (Taraxacum); Dandelion (Taraxacumofficinale); Germander (Teucrium cubense); Greenthread (Thelespermafilifolium); Pennycress, Field (Thlaspi arvense); Gray Tidestrom(Tidestromia lanuginosa); Hedge Parsley (Torilis arvensis); WesternSalsify (Tragopogon dubuis); Horse purslane (Trianthema portulacastrum);Puncturevine (Tribulus terrestris); Coat Buttons (Tridax procumbens);Alsike Clover (Trifolium hybridum); Broadleaf signalgrass (Urochloaplatyphylla); Cowcockle (Vaccaria pyramidata); Common Mullein (Verbascumthapsus); Dakota Verbena (Verbena bipinnatifida); Cowpen Daisy(Verbesina encelioides); Corn Speedwell (Veronica arvensis); PurslaneSpeedwell (Veronica peregrina); vetch (Vicia spp.); volunteer adzukibean (Vigna angularis); cocklebur (Xanthium strumarium); AsiaticHawksbeard (Youngia japonica).

Preferably, such weeds include Amaranthus spp., Capsella spp., Ipomoeaspp., Sinapis spp., Solanum spp., Ambrosia spp., Carex spp., Juncusspp., Potentilla spp., Ranunculus spp., Vicia spp., Xanthium spp,Hordeum spp.

More preferably, such weeds include redroot pigweed (Amaranthusretroflexus); shepherd's purse (Capsella bursa-pastoris); Morningglory,ivyleaf (Ipomoea hederacea); wild mustard (Sinapis arvensis);nightshade, black (Solanum nigrum); common ragweed (Ambrosiaartemisiifolia); great ragweed (Ambrosia trifida); sedges (Carex spp.);toad rush (Juncus bufonlus); Canada Rush (Juncus Canadensis); soft rush(Juncus effuses); slender rush (Juncus tenuis); cinquefoil (Potentillaspp.); creeping buttercup (Ranunculus repens); vetch (Vicia spp.);cocklebur (Xanthium strumarium), barley grass (Hordeum leporinum).

The total amount of (A) and (B) is from 5% to 99% by weight of thecomposition.

The crystalline modification I of mesotrione may be present in thesynergistic herbicidal composition of the present invention in anysuitable amount, and is generally present in an amount of from about 1%to about 90% by weight of the composition, preferably from about 1% to80% by weight, more preferably from about 1% to about 70% by weight ofthe composition.

The crystalline modification I of mesosulfuron-methyl may be present inthe synergistic herbicidal composition in any suitable amount, and isgenerally present in an amount of from about 0.1% to about 90% by weightof the composition, preferably from about 1% to about 80% by weight,more preferably from about 1% to about 70% by weight of the composition,more preferably from about 1% to about 60%.

(A) and (B) may be employed in the composition, method or use of thepresent invention in any suitable weight ratio. The weight ratio of thecrystalline modification I of mesotrione and the crystallinemodification I of mesosulfuron-methyl in the composition may be in therange of from about 150:1 to about 1:50, preferably from about 100:1 toabout 1:25, more preferably from about 50:1 to about 1:10, morepreferably still from about 15:1 to about 1:3, preferably from about15:1 to about 1:1, about 10:1 to about 1:1, most preferably 10:1.

In general, the application rate of the active ingredients depends onsuch factors as the type of weed, type of crop plant, soil type, season,climate, soil ecology and various other factors. The application rate ofthe composition for a given set of conditions can readily be determinedby routine trials.

In general the composition or the method of the present invention can beapplied at an application rate of from about 0.005 kilograms/hectare(kg/ha) to about 5.0 kg/ha of the total amount of active ingredient (A)and (B) being applied. Preferably, the application rate is from about0.01 kg/ha to 3.0 kg/ha of the active ingredients.

Preferably, the application rate of the active ingredients is from 1 to1000 g/ha of (A) the crystalline modification I of mesotrione and from0.1 to 250 g/ha of (B) the crystalline modification I ofmesosulfuron-methyl. More preferably, the application rate of the activeingredients is from 1 to 250 g/ha of (A) the crystalline modification Iof mesotrione and from 1 to 100 g/ha of (B) the crystalline modificationI of mesosulfuron-methyl. Even more preferably, the application rate ofthe active ingredients is from 1 to 200 g/ha of (A) the crystallinemodification I of mesotrione and from 1 to 75 g/ha of (B) thecrystalline modification I of mesosulfuron-methyl.

As noted above, in an embodiment of the invention, (A) the crystallinemodification I of mesotrione and (B) the crystalline modification I ofmesosulfuron-methyl may be applied either separately or combined as partof a two-part herbicidal system, such as the composition of the presentinvention. The composition is applied pre-planting, pre-emergence and/orpost-emergence.

The compositions of an embodiment of this invention can be formulated inconventional manner, for example by mixing (A) the crystallinemodification I of mesotrione and (B) the crystalline modification I ofmesosulfuron-methyl with appropriate auxiliaries. Suitable auxiliarieswill depend upon such factors as the type of formulation and will beknown to the person skilled in the art.

In particular, the composition may further comprise one or moreauxiliaries selected from extenders, carriers, solvents, surfactants,stabilizers, anti-foaming agents, anti-freezing agents, preservatives,antioxidants, colorants, thickening agents, solid adherents, fillers,wetting agents, dispersing agents, lubricants, anticaking agents anddiluents. Such auxiliaries are known in the art and are commerciallyavailable. Their use in the formulation of the compositions of thepresent invention will be apparent to the person skilled in the art.

Suitable formulations for applying a combination of (A) and (B) includewater-soluble concentrates (SL), emulsifiable concentrates (EC),emulsions, oil in water (EW), micro-emulsions (ME), suspensionconcentrates (SC), oil-based suspension concentrates (OD), flowablesuspensions (FS), water-dispersible granules (WG), water-solublegranules (SG), wettable powders (WP), water soluble powders (SP),granules (GR), encapsulated granules (CG), fine granules (FG),macrogranules (GG), aqueous suspo-emulsions (SE), capsule suspensions(CS) and microgranules (MG). Preferred formulations are suspensionconcentrates (SC), water-dispersible granules (WG) and water-solublegranules (SG).

The composition may comprise one or more inert fillers. Such inertfillers are known in the art and available commercially. Suitablefillers include, for example, natural ground minerals, such as kaolins,aluminas, talc, chalk, quartz, attapulgite, montmorillonite, anddiatomaceous earth, or synthetic ground minerals, such as highlydispersed silicic acid, aluminum oxide, silicates, and calciumphosphates and calcium hydrogen phosphates. Suitable inert fillers forgranules include, for example, crushed and fractionated naturalminerals, such as calcite, marble, pumice, sepiolite, and dolomite, orsynthetic granules of inorganic and organic ground materials, as well asgranules of organic material, such as sawdust, coconut husks, corn cobs,and tobacco stalks, and mixtures thereof.

The composition may optionally include one or more surfactants which arepreferably non-ionic, cationic and/or anionic in nature and surfactantmixtures which have good emulsifying, dispersing and wetting properties,depending upon the active compound/compounds being formulated. Suitablesurfactants are known in the art and are commercially available.

Suitable anionic surfactants can be both so-called water-soluble soapsand water-soluble synthetic surface-active compounds. Soaps which may beused include the alkali metal, alkaline earth metal or substituted orunsubstituted ammonium salts of higher fatty acid (C₁₀ to C₂₂), forexample the sodium or potassium salt of oleic or stearic acid, or ofnatural fatty acid mixtures.

The surfactant may comprise an emulsifier, dispersant or wetting agentof ionic or nonionic type. Examples of such agents include salts ofpolyacrylic acids, salts of lignosulphonic acid, salts ofphenylsulphonic or naphthalenesulphonic acids, polycondensates ofethylene oxide with fatty alcohols or with fatty acids or with fattyamines, substituted phenols, especially alkylphenols, sulphosuccinicester salts, taurine derivatives, especially alkyltaurates, andphosphoric esters of polyethoxylated phenols or alcohols.

The presence of at least one surfactant is generally required when theactive compound and/or the inert carrier and/or auxiliary/adjuvant areinsoluble in water and the vehicle for the final application of thecomposition is water.

The composition may optionally further comprise one or more polymericstabilizers. Suitable polymeric stabilizers that may be used in thepresent invention include, but are not limited to, polypropylene,polyisobutylene, polyisoprene, copolymers of monoolefins and diolefins,polyacrylates, polystyrene, polyvinyl acetate, polyurethanes orpolyamides. Suitable stabilizers are known in the art and commerciallyavailable.

The surfactants and polymeric stabilizers mentioned above are generallybelieved to impart stability to the composition, in turn allowing thecomposition to be formulated, stored, transported and applied.

Suitable anti-foaming agents for use in the compositions include allsubstances which can normally be used for this purpose in agrochemicalcompositions. Suitable anti-foaming agents are known in the art and areavailable commercially. Particularly preferred antifoam agents aremixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids,such as the silicone anti-foaming agents available from GE or Compton.

Suitable solvents for use in the compositions may be selected from allcustomary organic solvents which thoroughly dissolve the activecompounds employed. Again, suitable organic solvents for (A) and (B) areknown in the art. The following may be mentioned as being preferred:N-methyl pyrrolidone, N-octyl pyrrolidone, cyclohexyl-1-pyrrolidone; anda mixture of paraffinic, isoparaffinic, cycloparaffinic and aromatichydrocarbons (available commercially as SOLVESSO™200). Suitable solventsare commercially available.

Suitable preservatives include all substances which can normally be usedfor this purpose in agrochemical compositions of this type and again arewell known in the art. Suitable examples that may be mentioned includePREVENTOL® (from Bayer AG) and PROXEL® (from Bayer AG).

The compositions may comprise an antioxidant. Suitable antioxidants areall substances which can normally be used for this purpose inagrochemical compositions, as is known in the art. Preference is givento butylated hydroxytoluene.

Suitable thickening agents for use in the compositions include allsubstances which can normally be used for this purpose in agrochemicalcompositions. Examples include xanthan gum, PVOH, cellulose and itsderivatives, clay hydrated silicates, magnesium aluminum silicates or amixture thereof. Again, such thickening agents are known in the art andavailable commercially.

The compositions may further comprise one or more solid adherents. Suchadherents are known in the art and available commercially. They includeorganic adhesives, including tackifiers, such as celluloses ofsubstituted celluloses, natural and synthetic polymers in the form ofpowders, granules, or lattices, and inorganic adhesives such as gypsum,silica, or cement.

In addition, depending upon the formulation, the composition accordingto the invention may also comprise water.

The formulated composition may for example be applied in spray form, forexample employing appropriate dilutions using a diluent, such as water.

In the method and use of an embodiment of the invention, the combinationof the active ingredients can be applied to the locus where control isdesired, such as to the leaves of plants and/or the surrounding soil, bya convenient method.

In the event, (A) and (B) are applied simultaneously in an embodiment ofthe invention, they may be applied as a composition containing (A) and(B), in which case (A) and (B) can be obtained from a separateformulation source and mixed together (known as a tank-mix,ready-to-apply, spray broth, or slurry), optionally with otherpesticides, or (A) and (B) can be obtained as a single formulationmixture source (known as a pre-mix, concentrate, formulated compound (orproduct)), and optionally mixed together with other pesticides.

In a preferred embodiment, the method and use of the present inventionemploy a composition according to the present invention.

The compositions according to an embodiment of the invention aredistinguished by the fact that they are especially well tolerated byplants being treated and are environmentally friendly.

Although the invention has been described with reference to preferredembodiments and examples thereof, the scope of the present invention isnot limited only to those described embodiments. As will be apparent topersons skilled in the art, modifications and adaptations to theabove-described invention can be made without departing from the spiritand scope of the invention, which is defined by the appended claims.

Embodiments of the present invention will now be described, forillustrative purposes only, by way of the following examples.

EXAMPLES Example 1 Preparation of the Crystalline Modification IMesotrione

The crystalline modification I of mesotrione was prepared according tothe method as mentioned in WO2006021743.

Mesotrione enolate suspension was filtered to remove any excess solidenolate. 50 mL of the filtered solution was placed in a reaction flaskand heated to 40° C. The pH of the solution was adjusted to 2.8 byadding 10% HCl over 20 minutes. The crystals were allowed to stir for 20minutes before isolation by filtration. The crystals were then washedwith water and sucked dry on the filter.

Example 2 Preparation of the Crystalline Modification II Mesotrione

The crystalline modification II of mesotrione was prepared according tothe method as mentioned in WO2006021743.

Mesotrione crystals were stirred with water in a reaction flask. The pHwas increased to 12 by adding NaOH. 1.5 mL of 10% HCl was added over 15minutes to reduce the pH of the solution to pH 4. Crystals wereobtained.

Example 3 Preparation of Amorphous Mesosulfuron-Methyl in Accordancewith the Disclosure of U.S. Pat. No. 5,648,315N-tert-butyl-5-bromomethyl-2-methoxycarbonylbenzenesulfonamide (ExampleA1 in U.S. Pat. No. 5,648,315)

A solution of 54.8 g (192 mmol) ofN-tert-butyl-2-methoxycarbonyl-5-methylbenzenesulfonamide in 420 mltetrachloromethane was heated at reflux for 6-8 hours under a nitrogenprotective-gas atmosphere, following addition of 36 g (202 mmol)N-bromosuccinimide and 0.5 g azobisisobutyronitrile (AIBN) withsimultaneous irradiation with a daylight lamp. The solution was thenfiltered and then washed in succession with sodium disulphide solution,sodium hydrogen carbonate solution and water, dried over Na₂SO₄ andevaporated to dryness under reduced pressure Crystallization of theresidue from diisopropyl ether/ethyl acetate yielded 41.9 g (57%) ofN-tert-butyl-5-bromomethyl-2-methoxycarbonylbenzenesulfonamide havingmelting point of 88° C.-90° C.

N-tert-Butyl-5-azidomethyl-2-methoxycarbonylbenzenesulfonamide (ExampleA2 in U.S. Pat. No. 5,648,315)

A solution of 25.5 g (70 mmol)N-tert-butyl-5-bromomethyl-2-methoxycarbonylbenzenesulfonamide and 5.9 g(90 mmol) sodium azide in 240 ml of ethanol was heated at reflux for 6hours. The solution was then evaporated to dryness and the residue wasextracted with water/ethyl acetate. Digestion of the crude product withdiisopropyl ether gave 16.6 g (72.5%) ofN-tert-butyl-5-azidomethyl-2-methoxycarbonylbenzenesulfonamide havingmelting point of 63° C.-65° C.

N-tert-Butyl-5-aminomethyl-2-methoxycarbonylbenzenesulfonamide (ExampleA3 in U.S. Pat. No. 5,648,315)

16.3 g (50 mmol) N-tert-butyl-5-azidomethyl-2-methoxycarbonylbenzenesulfonamide were dissolved in 300 ml of methanol and hydrogenatedover Pd/C (5%). The mixture was filtered and evaporated to dryness. Thecrude product obtained was purified by elution through a silica gelcolumn using ethyl acetate/methanol 4:1. 11.2 g (74%) ofN-tert-butyl-5-aminomethyl-2-methoxycarbonylbenzenesulfonamide wereobtained as a viscous oil.

N-tert-Butyl-5-acetamidomethyl-2-methoxycarbonylbenzenesulfonamide(Example A4 in U.S. Pat. No. 5,648,315)

0.63 g (8 mmol) of acetyl chloride dissolved in 10 ml of dichloromethanewas added dropwise to a solution, cooled to 0° C., of 2.01 g (6.7 mmol)of N-tert-butyl-5-aminomethyl-2-methoxycarbonylbenzenesulfonamide and0.93 ml (6.7 mmol) of triethylamine in 30 ml of dichloromethane, and themixture was then stirred at room temperature for 2 hours. The reactionsolution was washed with water, dried and evaporated to dryness underreduced pressure. 2.1 g (91%) ofN-tertbutyl-5-acetamidomethyl-2-methoxycarbonylbenzenesulfonamide areobtained as a viscous oil.

5-Acetamidomethyl-2-methoxycarbonylbenzenesulfonamide (Example A5 inU.S. Pat. No. 5,648,315)

A solution of 2.09 g (6.1 mmol) ofN-tert-butyl-5-acetamidomethyl-2-benzenesulfonamide in 25 ml oftrifluoroacetic acid was stirred at room temperature for 14 hours andthen evaporated to dryness, Crystallization of the residue from ethylacetate yielded 1.33 g (76%) of 5-acetamidomethyl-2-methoxycarbonylbenzenesulfonamide of melting point of 173° C.-175° C.

Methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate(Example A6 in U.S. Pat. No. 5,648,315)

0.69 g (4.54 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was addedat 0° C. to a suspension of 1.3 g (4.54 mmol) of5-acetamidomethyl-2-methoxycarbonyl benzenesulfonamide and 1.25 g (4.54mmol) of N-4,6-dimethoxypyrimidin-2-yl)phenylcarbamate in 20 ml ofacetonitrile. After 2 hours at room temperature, the mixture was dilutedwith water and diethyl ether, acidified to pH 1-2 with hydrochloricacid, and the resulting precipitate was filtered off and dried, 1.32 g(62%) of methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluatehaving melting point of 149° C.-150° C. were obtained.

Scheme 1. Synthesis of Mesosulfuron-Methyl

As shown in FIG. 4, the X-ray powder diffraction pattern of theresulting mesosulfuron-methyl products prepared above has no significantsignals, which indicates the mesosulfuron-methyl product prepared inaccordance with the disclosure of U.S. Pat. No. 5,648,315 is amorphous.

Example 4 Preparation of the Crystalline Modification I ofMesosulfuron-Methyl

Crystallization from 1,1-Dichloroethane

10 ml 1,1-dichloroethane was charged into the reactor to dissolve crude,amorphous mesosulfuron-methyl prepared in Example 3 under stirring. Thisprocess lasted for 2 hours under room temperature, and white solidprecipitate appeared. The mixture was then cooled down to 0° C.-5° C.and maintained at this temperature for 1 hour to allow completecrystallization. After that, the mixture was centrifuged. The filtercake was washed with 1,1-dichloroethane. The resulting solid was driedunder high vacuum to give crystals of pure mesosulfuron-methyl technical(Purity: 98%).

The crystals were characterized as being of the crystalline modificationI of mesosulfuron-methyl using DSC, IR spectrometry and X-ray powderdiffraction.

The IR spectrum of the crystalline modification I of mesosulfuron-methylis set out in FIG. 1. The IR spectrum exhibits characteristic peaks at3246.88, 2958.83, 1741.75 and 1712.06 cm⁻¹.

Differential scanning calorimetry (DSC) (FIG. 3) shows an endothermicmelting peak with onset at 188.8° C. and peak maximum at about 192.9° C.in FIG. 3.

The crystalline modification I of mesosulfuron-methyl has the X-raypowder diffractogram shown in FIG. 2 with the reflexes listed in Table 1below.

TABLE 1 Crystalline modification I 2 θ (°) d (Å)  5.41 ± 0.2 16.35 ±0.05  10.26 ± 0.2 8.62 ± 0.05 10.88 ± 0.2 8.13 ± 0.05 12.14 ± 0.2 7.29 ±0.05 16.38 ± 0.2 5.41 ± 0.05 18.87 ± 0.2 4.70 ± 0.05 19.47 ± 0.2 4.56 ±0.05 20.82 ± 0.2 4.27 ± 0.05 21.88 ± 0.2 4.06 ± 0.05 22.55 ± 0.2 3.94 ±0.05 22.96 ± 0.2 3.87 ± 0.05 23.22 ± 0.2 3.83 ± 0.05 24.10 ± 0.2 3.69 ±0.05 24.50 ± 0.2 3.63 ± 0.05 26.35 ± 0.2 3.38 ± 0.05

Example 5 Preparation of the Crystalline Modification I ofMesosulfuron-Methyl

Crystallization from Ethanol

10 ml ethanol was charged into the reactor to dissolve crude, amorphousmesosulfuron-methyl prepared in Example 3 under stirring. This processlasted for 2 hours under room temperature, and white solid precipitateappeared. The mixture was then cooled down to 0° C.-5° C. and maintainedat this temperature for 1 hour to allow complete crystallization. Afterthat, the mixture was centrifuged. The filter cake was washed with someethanol. The resulting solid was dried under high vacuum to givecrystals of pure mesosulfuron-methyl technical (Purity: 98%).

The crystals were characterized as being the crystalline modification Iof mesosulfuron-methyl using IR spectrometry, X-ray powder diffractionand DSC as described in Example 4.

Formulation Examples

Water-dispersible granule (WG) was prepared by mixing and milling ofactive ingredients and auxiliaries (0.5% SUPRALATE® (sodium laurylsulfate, Witco Inc., Greenwich), 5% REAX®88B (sodium lignosulfonate,Westvaco Corp), Potassium carbonate (balance to 100%)) under compressedair, then wetting, extruding and drying to obtain water-dispersiblegranule.

For example,

The crystalline modification I of mesotrione 50%

The crystalline modification I of mesosulfuron-methyl 10%

SUPRALATE® (sodium lauryl sulfate, Witco Inc., Greenwich) 0.5%

REAX®88B (sodium lignosulfonate, Westvaco Corp) 5%

Potassium carbonate Balance to 100%

Aqueous suspension concentrates (SC) were prepared by mixing finelyground active ingredients with auxiliaries (10% Propylene glycol, 5%Tristyrylphenol ethoxylates, 1% Sodium lignosulfonate, 1%Carboxymethylcellulose, 1% Silicone oil (in the form of a 75% emulsionin water), 0.1% Xanthan gum, 0.1% NIPACIDE BIT 20, Water (Balance to 1L).

For example,

The crystalline modification I of mesotrione 40%

The crystalline modification I of mesosulfuron-methyl 4%

Propylene glycol 10%

Tristyrylphenol ethoxylates 5%

Sodium lignosulfonate 1%

Carboxymethylcellulose 1%

Silicone oil (in the form of a 75% emulsion in water) 1%

Xanthan gum 0.1%

NIPACIDE BIT 20 0.1%

Water Balance to 100%

Water-soluble granules (SG) was prepared by mixing and milling of activeingredients and auxiliaries (0.5% SUPRALATE® (sodium lauryl sulfate,Witco Inc., Greenwich), 5% REAX®88B (sodium lignosulfonate, WestvacoCorp), 2% Sodium hydrogen carbonate (NaHCO₃), Potassium sulfate (balanceto 100%)) under compressed air, then wetting, extruding and drying toobtain water-soluble granules.

For example,

The crystalline modification I of mesotrione 30%

The crystalline modification I of mesosulfuron-methyl 2%

SUPRALATE® (sodium lauryl sulfate, Witco Inc., Greenwich) 0.5%

REAX® 88B (sodium lignosulfonate, Westvaco Corp) 5%

Sodium hydrogen carbonate (NaHCO₃) 2%

Potassium sulfate Balance to 100%

Formulations were prepared according to the method above (Table A):

TABLE A Formulation Mesotrione (%) Mesosulfuron-methyl (%) No. type I IIAmorphous I 1 SC 40 / / / 2 SC / 40 / / 3 WG / / 60  / 4 WG / / / 60 5SC 40 / 4 / 6 SC / 40 4 / 7 SC 40 / /  4 8 SC / 40 /  4 9 SC 40 / /  410 WG 50 / / 10 11 SC 40 / /  8 12 SG 30 / /  2 13 WG 60 / /  6 14 SC 20/ / 20 15 SG 10 / / 30

Biological Examples 1

A synergistic effect exists with a combination of two active compoundswhen the activity of a composition comprising both active compounds isgreater than the sum of the activities of the two active compoundsapplied individually. The expected activity for a given combination oftwo active compounds can be calculated by the so called “Colby equation”(see S. R. Colby, “Calculating Synergistic and Antagonistic Responses ofHerbicide Combinations”, Weeds 1967, 15, 20-22):

whereby:

A=the efficiency % of compound A when active compound A is employed atan application rate of m g/ha;

B=the efficiency % of compound B when active compound B is employed atan application rate of n g/ha;

E=the efficiency % of estimated activity when compounds A and B areemployed together at an application rate of m g/ha and n g/ha;

then:E=A+B−(A×B/100).

If the actual activity observed for the combination of compounds A and Bis greater than that calculated, then the activity of the combination issuperadditive. In other words, synergism is present.

Wheat and corn and sorghum plants were sown side by side in the field.Different types of weeds and their relative density were recorded andare listed in Table 1 below. Formulations of Examples 1 to 8 above wereapplied 50 days after planting. After application, the beds weremaintained for about 2 weeks. Two weeks after application, the beds wereexamined to determine the efficiency of the treatment. The results areset forth below in Table 2 below.

TABLE 1 Type of weed Type of weed Relative density (%) Redroot pigweed(Amaranthus retroflexus) 25 Cocklebur (Xanthium strumarium) 15 Commonragweed (Ambrosia artemisiifolia) 10 Shepherd's Purse (Capsellabursa-pastoris) 10 Morningglory, ivyleaf (Ipomoea hederacea) 15 Barleygrass (Hordeum leporinum); 25

TABLE 2 Efficiency (%) Efficiency (%) Type of weed Mesosulfuron-Formulation Mesotrione methyl Redroot Common Shepherd's Morningglory,Barley Examples (g/ha) (g/ha) pigweed Cocklebur ragweed Purse ivyleafgrass Untreated 0 0 0 0 0 0 0 0 Example 1 100 0 40 25 25 35 40 35Example 2 100 0 40 25 30 35 45 35 Example 3 0 10 35 20 20 30 35 45Example 4 0 10 30 20 20 35 35 50 Example 5 100 10 55 35 35 40 50 45Example 6 100 10 35 30 35 35 40 35 Example 7 100 10 95 90 95 90 100 95Example 8 100 10 45 40 40 45 50 55

Biological Examples 2

Asparagus, cranberry and blueberry plants were sown side by side in thefield. Different types of weeds and their relative density were recordedand are listed in Table 3 below. Formulations of Examples 9 to 15 abovewere applied 50 days after planting. After application, the beds weremaintained for about 2 weeks. Two weeks after application, the beds wereexamined to determine the efficiency of the treatment. The results areset forth below in Table 4 below.

TABLE 3 Type of weed Type of weed Relative density (%) Toad rush (Juncusbufonlus)  5 Cinquefoil (Potentilla spp.)  5 Great ragweed (Ambrosiatrifida) 15 Vetch (Vicia spp.) 15 Wild mustard (Sinapis arvensis) 10Nightshade, black (Solanum nigrum) 15 Sedges (Carex spp.)  5 Canada Rush(Juncus Canadensis) 10 Soft rush (Juncus effuses)  5 Slender rush(Juncus tenuis)  5 Creeping buttercup (Ranunculus repens) 10

Efficiency (%) Efficiency (%) Type of weed Formulation MesotrioneMesosulfuron- Toad Great Wild Nightshade, Canada Soft Slender CreepingExamples (g/ha) methyl (g/ha) rush Cinquefoil ragweed Vetch mustardblack Sedges Rush rush rush buttercup Untreated 0 0 0 0 0 0 0 0 Example9 100 10 100 95 90 95 95 100 90 95 100 100 100 Example 10 125 25 100 9590 90 95 100 95 90 100 95 95 Example 11 100 20 95 95 95 90 90 100 90 95100 100 95 Example 12 75 5 95 95 90 90 95 95 90 95 95 100 90 Example 13150 15 100 95 95 90 90 95 90 100 95 100 100 Example 14 50 50 95 90 90 9595 95 90 95 95 95 95 Example 15 25 75 90 90 90 95 95 90 95 95 90 95 90

The invention claimed is:
 1. A composition comprising a herbicidallyeffective amount of (A) the crystalline modification I of2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione (mesotrione); and (B)the crystalline modification I of methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate(mesosulfuron-methyl), wherein the crystalline modification I ofmesosulfuron-methyl is crystallized using 1,1-dichloroethane and/orethanol, and the crystalline modification I of mesosulfuron-methylexhibits each of the following reflexes as 2θ values in an X-ray powderdiffractogram recorded using Cu-Kα radiation at 25° C.:2θ=5.41±0.2  (1)2θ=10.26±0.2  (2)2θ=10.88±0.2  (3)2θ=12.14±0.2  (4)2θ=16.38±0.2  (5)2θ=18.87±0.2  (6)2θ=19.47±0.2  (7)2θ=20.82±0.2  (8)2θ=21.88±0.2  (9)2θ=22.55±0.2  (10)2θ=22.96±0.2  (11)2θ=23.22±0.2  (12)2θ=24.10±0.2  (13)2θ=24.50±0.2  (14)2θ=26.35±0.2  (15).
 2. The composition according to claim 1, wherein theweight ratio of (A) to (B) is in the range of from about 150:1 to about1:50.
 3. The composition according to claim 2, wherein the weight ratioof (A) to (B) is in the range of from about 50:1 to about 1:10.
 4. Thecomposition according to claim 3, wherein the weight ratio of (A) to (B)is 10:1.
 5. The composition according to claim 1, wherein the totalamount of (A) and (B) is from 5% to 99% by weight of the composition. 6.The composition according to claim 5, wherein the composition comprises,by weight, from about 1% to about 90% of (A) and from about 0.1% toabout 90% of (B).
 7. The composition according to claim 5, wherein thecomposition comprises, by weight, from about 1% to about 70% of (A) andfrom about 1% to about 60% of (B).
 8. The composition according to claim1, further comprising one or more auxiliaries selected from the groupconsisting of extenders, carriers, solvents, surfactants, stabilizers,anti-foaming agents, anti-freezing agents, preservatives, antioxidants,colorants, thickening agents, solid adherents, fillers, wetting agents,dispersing agents, lubricants, anticaking agents and diluents.
 9. Thecomposition according to claim 1, formulated as a water-solubleconcentrate (SL), an emulstifiable concentrate (EC), an emulsion, oil inwater (EW), a micro-emulsion (ME), a suspension concentrate (SC), anoil-based suspension concentrate (OD), a flowable suspension (FS), awater-dispersible granule (WG), a water-soluble granule (SG), a wettablepowder (WP), a water soluble powder (SP), a granule (GR), anencapsulated granule (CG), a fine granule (FG), a macrogranule (GG), anaqueous suspo-emulsion (SE), a capsule suspension (CS) or a microgranule(MG).
 10. A method of controlling undesirable plant growth comprisingapplying to the plant or to the locus thereof a herbicidally effectiveamount of the herbicidal composition of claim
 1. 11. The methodaccording to claim 10, wherein the plant growth is being controlled in acrop comprising cereals, fruits and vegetables.
 12. The method accordingto claim 10, wherein the plant growth being controlled is one or more ofbroadleaf weeds, grasses and sedges.
 13. The method according to claim12, wherein the plant growth being controlled is one or more ofAmaranthus spp., Capsella spp., Ipomoea spp., Sinapis spp., Solanumspp., Ambrosia spp., Carex spp., Juncus spp., Potentilla spp.,Ranunculus spp., Vicia spp., Xanthium spp, and Hordeum spp.
 14. Themethod according to claim 10, wherein the composition is applied at anapplication rate of about 0.005 kilograms/hectare (kg/ha) to about 5.0kg/ha of the total amount of active ingredient (A) and (B).
 15. Themethod according to claim 14, wherein the composition is applied at anapplication rate of from 0.01 kg/ha to 3.0 kg/ha of the total amount ofactive ingredient (A) and (B).
 16. The method according to claim 15,wherein the composition is applied at an application rate of from 1 to1000 g/ha of (A) and from 0.1 to 250 g/ha of (B).
 17. The methodaccording to claim 16, wherein the composition is applied at anapplication rate of from 1 to 200 g/ha of (A) and 1 to 75 g/ha of (B).18. The method according to claim 10, wherein the composition is appliedpre-planting, pre-emergence and/or post-emergence.
 19. A method ofcontrolling undesirable plant growth at a locus comprising applying tothe locus herbicidally effective amounts of (A) the crystallinemodification I of 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione(mesotrione) and (B) the crystalline modification I of methyl2-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-α-(methanesulfonamido)-p-toluate(mesosulfuron-methyl), wherein the crystalline modification I ofmesosulfuron-methyl is crystallized using 1,1-dichloroethane and/orethanol, and the crystalline modification I of mesosulfuron-methylexhibits each of the following reflexes as 20 values in an X-ray powderdiffractogram recorded using Cu-Kα radiation at 25° C.:2θ=5.41±0.2  (1)2θ=10.26±0.2  (2)2θ=10.88±0.2  (3)2θ=12.14±0.2  (4)2θ=16.38±0.2  (5)2θ=18.87±0.2  (6)2θ=19.47±0.2  (7)2θ=20.82±0.2  (8)2θ=21.88±0.2  (9)2θ=22.55±0.2  (10)2θ=22.96±0.2  (11)2θ=23.22±0.2  (12)2θ=24.10±0.2  (13)2θ=24.50±0.2  (14)2θ=26.35±0.2  (15).
 20. The method according to claim 19, wherein theplant growth is being controlled in a crop comprising cereals, fruitsand vegetables.
 21. The method according to claim 19, wherein (A) and(B) are applied to the locus at the same time.
 22. The method accordingto claim 19, wherein (A) and (B) are applied to the locus consecutively.23. The method according to claim 19, wherein the plant growth beingcontrolled is one or more of broadleaf weeds, grasses and sedges. 24.The method according to claim 23, wherein the plant growth beingcontrolled is one or more of Amaranthus spp., Capsella spp., Ipomoeaspp., Sinapis spp., Solanum spp., Ambrosia spp., Carex spp., Juncusspp., Potentilla spp., Ranunculus spp., Vicia spp., Xanthium spp andHordeum spp.
 25. The method according to claim 19, wherein the weightratio of (A) to (B) applied is in the range of from about 150:1 to about1:50.
 26. The method according to claim 25, wherein the weight ratio of(A) to (B) applied is in the range of from about 50:1 to about 1:10. 27.The method according to claim 26, wherein the weight ratio of (A) to (B)applied is 10:1.
 28. The method according to claim 19, wherein (A) and(B) are applied at an application rate of 0.005 kilograms/hectare(kg/ha) to about 5.0 kg/ha of the total amount of active ingredient (A)and (B).
 29. The method according to claim 28, wherein (A) and (B) areapplied at an application rate of from about 0.01 kg/ha to about 3.0kg/ha of the total amount of active ingredient (A) and (B).
 30. Themethod according to claim 29, wherein (A) and (B) are applied at anapplication rate of from 1 to 1000 g/ha of (A) and from 0.1 to 250 g/haof (B).
 31. The method according to claim 30, wherein (A) and (B) areapplied at an application rate of from 1 to 200 g/ha of (A) and 1 to 75g/ha of (B).
 32. The method according to claim 19, wherein (A) and (B)are applied pre-planting, pre-emergence and/or post-emergence.